Salt compositions for explosives

ABSTRACT

Salt compositions are disclosed which comprise: (A) at least one salt moiety derived from (A)(I) at least one high-molecular weight polycarboxylic acylating agent, said acylating agent (A)(I) having at least one hydrocarbyl substituent having an average of from about 20 to about 500 carbon atoms, and (A)(II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; (B) at least one salt moiety derived from (B)(I) at least one low-molecular weight polycarboxylic acylating agent, said acylating agent (B)(I) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms, and (B)(II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; said components (A) and (B) being coupled together by (C) at least one compound having (i) two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and at least one secondary amino group, (iv) at least two hydroxyl groups or (v) at least one primary or secondary amino group and at least one hydroxyl group. These salt compositions are useful as emulsifiers in water-in-oil explosive emulsions, particularly cap-sensitive explosive emulsions.

TECHNICAL FIELD

This invention relates to novel salt compositions and to explosivecompositions comprising said salt compositions. The salt compositionsare useful as emulsifiers in the explosive compositions. The explosivecompositions are water-in-oil explosive emulsions which, in oneembodiment, are cap-sensitive explosive emulsions.

BACKGROUND OF THE INVENTION

Hydrocarbyl-substituted carboxylic acylating agents having at leastabout 30 aliphatic carbon atoms in the substituent are known. Examplesof such acylating agents include the polyisobutenyl-substituted succinicacids and anhydrides. The use of such carboxylic acylating agents asadditives in normally liquid fuels and lubricants is disclosed in U.S.Pat. Nos. 3,288,714 and 3,346,354. These acylating agents are alsouseful as intermediates for preparing additives for use in normallyliquid fuels and lubricants as described in U.S. Pat. Nos. 2,892,786;3,087,936; 3,163,603; 3,172,892; 3,189,544; 3,215,707; 3,219,666;3,231,587; 3,235,503; 3,272,746; 3,306,907; 3,306,908; 3,331,776;3,341,542; 3,346,354; 3,374,174; 3,379,515; 3,381,022; 3,413,104;3,450,715; 3,454,607; 3,455,728; 3,476,686; 3,513,095; 3,523,768;3,630,904; 3,632,511; 3,697,428; 3,755,169; 3,804,763; 3,836,470;3,862,981; 3,936,480; 3,948,909; 3,950,341; 4,234,435; and 4,471,091;and French Patent No. 2,223,415.

U.S. Pat. No. 3,216,936 describes nitrogen-containing dispersants foruse in lubricants which are obtained by the reaction of an alkyleneamine with an acidic mixture consisting of a hydrocarbon-substitutedsuccinic acid having at least about 50 aliphatic carbon atoms in thehydrocarbon substituent and an aliphatic monocarboxylic acid. Thealiphatic monocarboxylic acids are described as including saturated andunsaturated acids such as acetic acid, dodecanoic acid, oleic acid,naphthenic acid, formic acid, etc. Acids having 12 or more aliphaticcarbon atoms, particularly stearic acid and oleic acid, are described asbeing especially useful.

U.S. Pat. Nos. 3,639,242 and 3,708,522 describe compositions prepared bypost-treating mono- and polycarboxylic acid esters with mono- orpolycarboxylic acid acylating agents. The compositions thus obtained arereported to be useful as dispersants in lubricants and fuels.

U.S. Pat. No. 4,642,330 discloses dispersant salt compositions made byreacting phosphorus-free carboxylic solubilizers with sulfonic acid-freeorganic acids or mineral acids. The carboxylic solubilizer is thereaction product of a polycarboxylic acid acylating agent having atleast one hydrocarbon-based substituent of at least 8 to 500 carbonatoms with at least one poly(alkyleneamine). The reference indicatesthat these dispersant salt compositions have good thermal stability whenmixed with a surfactant or a hydrophilic organic solvent, and that theycan be used with aqueous solutions to disperse various fillers includingcarbon black and to solubilize various fluids.

Nitrogen-containing, phosphorus-free carboxylic solubilizers useful inwater based functional fluids are disclosed in U.S. Pat. Nos. 4,329,249;4,368,133; 4,435,297; 4,447,348; and 4,448,703. These solubilizers aremade by reacting (I) at least one carboxylic acid acylating agent havingat least one hydrocarbyl substituent of from about 12 to about 500carbon atoms with (II) at least one (a) N-(hydroxyl-substitutedhydrocarbyl) amine, (b) hydroxyl-substituted poly(hydrocarbyloxy) analogof said amine (a), or (c) mixtures of (a) and (b). These patentsindicate that preferred acylating agents include the substitutedsuccinic acids or anhydrides, such as polyisobutenyl-substitutedsuccinic anhydride, and that the amines that are useful include theprimary, secondary and tertiary alkanol amines, such asdiethylethanolamine and mixtures of diethylethanolamine andethanolamine. These solubilizers are useful in dispersing oil-soluble,water-insoluble functional additives in water-based functional fluids.

Water-in-oil explosive emulsions typically comprise a continuous organicphase and a discontinuous oxidizer phase containing water and anoxygen-supplying source such as ammonium nitrate, the oxidizer phasebeing dispersed throughout the continuous organic phase. Examples ofsuch water-in-oil explosive emulsions are disclosed, inter alia, in U.S.Pat. Nos. 3,447,978; 3,765,964; 3,985,593; 4,008,110; 4,097,316;4,104,092; 4,218,272; 4,259,977; 4,357,184; 4,371,408; 4,391,659;4,404,050; 4,409,044; 4,448,619; 4,453,989; and 4,534,809; U.K. PatentApplication GB No. 2,050,340A; and European Application Publication No.0,156,572.

European Application No. 0,155,800 discloses an explosive emulsioncomposition comprising a discontinous phase containing anoxygen-supplying component and an organic medium forming a continuousphase wherein the oxygen-supplying component and organic medium arecapable of forming an emulsion which, in the absence of a supplementaryadjuvant, exhibits an electrical conductivity measured at 60° C., notexceeding 60,000 picomhos/meter. The reference indicates that theconductivity may be achieved by the inclusion of a modifier which alsofunctions as an emulsifier. The modifier is comprised of a hydrophilicmoiety and a lipophilic moiety. The lipophilic moiety can be derivedfrom a poly[alk(en)yl] succinic anhydride. Poly(isobutylene) succinicanhydride having a number average molecular weight in the range of 400to 5000 is specifically identified as being useful. The hydrophilicmoiety is described as being polar in character, having a molecularweight not exceeding 450 and can be derived from polyols, amines,amides, alkanol amines and heterocyclics. Example 14 of this referencediscloses the use of a 1:1 condensate polyisobutenyl succinic anhydride(number average molecular weight=1200) and N, N-dimethylamino ethanol asthe modifier.

Cap-sensitive explosive emulsions are water-in-oil explosive emulsionswhich can be detonated without the use of a booster. Examples of suchcap-sensitive explosive emulsions are disclosed, inter alia, in U.S.Pat. Nos. 3,715,247; 4,110,134; 4,149,916; 4,149,917; 4,231,821;3,383,873; 4,394,198; and 4,490,195.

SUMMARY OF THE INVENTION

The present invention provides for a novel salt composition comprising:(A) at least one salt moiety derived from (A)(I) at least onehigh-molecular weight polycarboxylic acylating agent, said acylatingagent (A)(I) having at least one hydrocarbyl substituent having anaverage of from about 20 to about 500 carbon atoms, and (A)(II) ammonia,at least one amine, at least one alkali or alkaline earth metal, and/orat least one alkali or alkaline earth metal compound; (B) at least onesalt moiety derived from (B)(I) at least one low-molecular weightpolycarboxylic acylating agent, said acylating agent (B)(I) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms, and (B)(II) ammonia, at least one amine, at leastone alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound; said components (A) and (B) being coupledtogether by (C) at least one compound having (i) two or more primaryamino groups, (ii) two or more secondary amino groups, (iii) at leastone primary amino group and at least one secondary amino group, (iv) atleast two hydroxyl groups or (v) at least one primary or secondary aminogroup and at least one hydroxyl group. These salt compositions areuseful as emulsifiers in water-in-oil explosive emulsions, particularlycap-sensitive water-in-oil explosive emulsions.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "emulsion" as used in this specification and in the appendedclaims is intended to cover not only water-in-oil emulsions, but alsocompositions derived from such emulsions wherein at temperatures belowthat at which the emulsion is formed the discontinuous phase is solid orin the form of droplets of super-cooled liquid. This term also coverscompositions derived from or formulated as such water-in-oil emulsionsthat are in the form of gelatinous or semi-gelatinous compositions.

The term "hydrocarbyl" is used herein to include:

(1) hydrocarbyl groups, that is, aliphatic (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted aromatic groups and the like as well as cyclicgroups wherein the ring is completed through another portion of themolecule (that is, any two indicated groups may together form analicyclic group);

(2) substituted hydrocarbyl groups, that is, those groups containingnon-hydrocarbon groups which, in the context of this invention, do notalter the predominantly hydrocarbyl nature of the hydrocarbyl group;those skilled in the art will be aware of such groups, examples of whichinclude ether, oxo, halo (e.g., chloro and fluoro), alkoxyl, mercapto,alkylmercapto, nitro, nitroso, sulfoxy, etc.;

(3) hetero groups, that is, groups which, while having predominantlyhydrocarbyl character within the context of this invention, containother than carbon in a ring or chain otherwise composed of carbon atoms.Suitable heteroatoms will be apparent to those of skill in the art andinclude, for example, sulfur, oxygen, nitrogen and such substituents aspyridyl, furanyl, thiophenyl, imidazolyl, etc.

In general, no more than about three nonhydrocarbon groups orheteroatoms and preferably no more than one, will be present for eachten carbon atoms in a hydrocarbyl group. Typically, there will be nosuch groups or heteroatoms in a hydrocarbyl group and it will,therefore, be purely hydrocarbyl.

The hydrocarbyl groups are preferably free from acetylenic unsaturation;ethylenic unsaturation, when present will generally be such that thereis no more than one ethylenic linkage present for every tencarbon-to-carbon bonds. The hydrocarbyl groups are often completelysaturated and therefore contain no ethylenic unsaturation.

The term "lower" as used herein in conjunction with terms such as alkyl,alkenyl, alkoxy, and the like, is intended to describe such groups whichcontain a total of up to 7 carbon atoms.

Components (A)(I) and (B)(I)

The carboxylic acylating agents (A)(I) and (B)(I) are aliphatic oraromatic, polycarboxylic acids or acid-producing compounds. Throughoutthis specification and in the appended claims, the term "carboxylicacylating agent" is intended to include carboxylic acids as well asacid-producing derivatives thereof such as anhydrides, esters, acylhalides and mixtures thereof, unless otherwise specifically stated.

The acylating agents (A)(I) and (B)(I) may contain polar substituentsprovided that the polar substituents are not present in portionssufficiently large to alter significantly the hydrocarbon character ofthe acylating agent. Typical suitable polar substituents include halo,such as chloro and bromo, oxo, oxy, formyl, sulfenyl, sulfinyl, thio,nitro, etc. Such polar substituents, if present, preferably do notexceed about 10% by weight of the total weight of the hydrocarbonportion of the acylating agent, exclusive of the carboxyl groups.

Examples of low molecular weight polycarboxylic acids (B)(I) includedicarboxylic acids and derivatives such as maleic acid, maleicanhydride, chloromaleic anhydride, malonic acid, succinic acid, succinicanhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid,azelaic acid, sebacic acid, glutaconic acid, citraconic acid, itaconicacid, allyl succinic acid, cetyl malonic acid,tetrapropylene-substituted succinic anhydride, etc. Lower alkyl estersof these acids can also be used.

Low molecular weight hydrocarbyl-substituted succinic acid andanhydrides can also be used. These succinic acids and anhydrides can berepresented by the formulae ##STR1## wherein R is a C₁ to about a C₁₈hydrocarbyl group. Preferably, R is an aliphatic or alicyclichydrocarbyl group with less than about 10% of its carbon-to-carbon bondsbeing unsaturated. R can be derived from olefins of from 2 to about 18carbon atoms with alpha-olefins being particularly useful. Examples ofsuch olefins include ethylene, propylene, 1-butene, isobutene,1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 1-heptene,1-octene, styrene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, etc. Commercially available alpha olefin fractions such asC₁₅₋₁₈ alpha-olefins, C₁₂₋₁₆ alpha-olefins, C₁₄₋₁₆ alpha-olefins, C₁₄₋₁₈alpha-olefins, C₁₆₋₁₈ alpha-olefins, etc., are particularly useful;these commercial alpha-olefin fractions also usually include minoramounts of alpha-olefins outside the given ranges. The production ofsuch substituted succinic acids and their derivatives is well known tothose of skill in the art and need not be discussed in detail herein.

Acid halides of the afore-described low-molecular weight polycarboxylicacids can be used as the low-molecular weight acylating agents (B)(I) ofthis invention. These can be prepared by the reaction of such acids ortheir anhydrides with halogenating agents such as phosphorus tribromide,phosphorus pentachloride, phosphorus oxychloride or thionyl chloride.Esters of such acids can be prepared simply by the reaction of the acid,acid halide or anhydride with an alcohol or phenolic compound.Particularly useful are the lower alkyl and alkenyl alcohols such asmethanol, ethanol, allyl alcohol, propanol, cyclohexanol, etc.Esterification reactions are usually promoted by the use of alkalinecatalysts such as sodium hydroxide or alkoxide, or an acidic catalystsuch as sulfuric acid or toluene sulfonic acid.

Although it is preferred that the acylating agent (B)(I) is an aliphaticpolycarboxylic acid, and more preferably a dicarboxylic acid, thecarboxylic acylating agent (B)(I) may also be an aromatic polycarboxylicacid or acid-producing compound. The aromatic acids are preferablydicarboxy-substituted benzene, naphthalene, anthracene, phenanthrene orlike aromatic hydrocarbons. They include also the alkyl-substitutedderivatives, and the alkyl groups may contain up to about 12 carbonatoms. The aromatic acid may also contain other substituents such ashalo, hydroxy, lower alkoxy, etc. Specific examples of aromaticpolycarboxylic acids and acid-producing compounds useful as acylatingagent (B)(I) include phthalic acid, isophthalic acid, terephthalic acid,4-methyl-benzene-1,3-dicarboxylic acid, naphthalene-1,4-dicarboxylicacid, anthracene dicarboxylic acid, 3-dodecyl-benzene-1,4-dicarboxylicacid, 2,5-dibutylbenzene-1,4-dicarboxylic acid, etc. The anhydrides ofthese dicarboxylic acids also are useful as the carboxylic acylatingagent (B)(I).

The high-molecular weight polycarboxylic acylating agents (A)(I) arewell known in the art and have been described in detail, for example, inthe following U.S., British and Canadian patents: U.S. Pat. Nos.3,024,237; 3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666;3,231,587; 3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746;3,278,550; 3,288,714; 3,306,907; 3,307,928; 3,312,619; 3,341,542;3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179;3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169;3,868,330; 3,912,764; 4,234,435; and 4,368,133; British Patent Nos.944,136; 1,085,903; 1,162,436; and 1,440,219; and Canadian Patent No.956,397. These patents are incorporated herein by reference.

As disclosed in the foregoing patents, there are several processes forpreparing these high-molecular weight acylating agents (A)(I).Generally, these processes involve the reaction of (1) an ethylenicallyunsaturated carboxylic acid, acid halide, anhydride or ester reactantwith (2) an ethylenically unsaturated hydrocarbon containing at leastabout 20 aliphatic carbon atoms or a chlorinated hydrocarbon containingat least about 20 aliphatic carbon atoms at a temperature within therange of about 100°-300° C. The chlorinated hydrocarbon or ethylenicallyunsaturated hydrocarbon reactant preferably contains at least about 30carbon atoms, more preferably at least about 40 carbon atoms, morepreferably at least about 50 carbon atoms, and may contain polarsubstituents, oil-solubilizing pendant groups, and be unsaturated withinthe general limitations explained hereinabove.

When preparing the carboxylic acid acylating agent, the carboxylic acidreactant usually corresponds to the formula R_(o) --(COOH)_(n), whereR_(o) is characterized by the presence of at least one ethylenicallyunsaturated carbon-to-carbon covalent bond and n is an integer from 2 toabout 6 and preferably is 2. The acidic reactant can also be thecorresponding carboxylic acid halide, anhydride, ester, or otherequivalent acylating agent and mixtures of two or more of these.Ordinarily, the total number of carbon atoms in the acidic reactant willnot exceed about 20, preferably this number will not exceed about 10 andgenerally will not exceed about 6, exclusive of the carboxyl-basedgroups. Preferably the acidic reactant will have at least one ethyleniclinkage in an alpha, beta-position with respect to at least one carboxylfunction. Exemplary acidic reactants are maleic acid, maleic anhydride,fumaric acid, itaconic acid, itaconic anhydride, citraconic acid,citraconic anhydride, mesaconic acid, chloromaleic acid, aconitic acid,and the like. Preferred acid reactants include maleic acid and maleicanhydride.

The ethylenically unsaturated hydrocarbon reactant and the chlorinatedhydrocarbon reactant used in the preparation of these high-molecularweight carboxylic acylating agents (A)(I) are preferably high molecularweight, substantially saturated petroleum fractions and substantiallysaturated olefin polymers and the corresponding chlorinated products.Polymers and chlorinated polymers derived from mono-olefins having from2 to about 30 carbon atoms are preferred. Especially useful polymers arethe polymers of 1-mono-olefins such as ethylene, propene, 1-butene,isobutene, 1-hexene, 1-octene, 2-methyl- 1-heptene,3-cyclohexyl-1-butene, and 2-methyl-5-propyl-1-hexene. Polymers ofmedial olefins, i.e., olefins in which the olefinic linkage is not atthe terminal position, likewise are useful. These are exemplified by2-butene, 3-pentene, and 4-octene.

Interpolymers of 1-mono-olefins such as illustrated above with eachother and with other interpolymerizable olefinic substances such asaromatic olefins, cyclic olefins, and polyolefins, are also usefulsources of the ethylenically unsaturated reactant. Such interpolymersinclude for example, those prepared by polymerizing isobutene withstyrene, isobutene with butadiene, propene with isoprene, propene withisobutene, ethylene with piperylene, isobutene with chloroprene,isobutene with p-methyl-styrene, 1-hexene with 1,3-hexadiene, 1-octenewith 1-hexene, 1-heptene with 1-pentene, 3-methyl-1-butene with1-octene, 3,3-dimethyl-1-pentene with 1-hexene, isobutene with styreneand piperylene, etc.

For reasons of hydrocarbon solubility, the interpolymers contemplatedfor use in preparing the acylating agents of this invention arepreferably substantially aliphatic and substantially saturated, that is,they should contain at least about 80% and preferably about 95%, on aweight basis, of units derived from aliphatic mono-olefins. Preferably,they will contain no more than about 5% olefinic linkages based on thetotal number of the carbon-to-carbon covalent linkages present.

In one embodiment of the invention, the polymers and chlorinatedpolymers are obtained by the polymerization of a C₄ refinery streamhaving a butene content of about 35% to about 75% by weight and anisobutene content of about 30% to about 60% by weight in the presence ofa Lewis acid catalyst such as aluminum chloride or boron trifluoride.These polyisobutenes preferably contain predominantly (that is, greaterthan about 80% of the total repeat units) isobutene repeat units of theconfiguration. ##STR2##

The chlorinated hydrocarbons and ethylenically unsaturated hydrocarbonsused in the preparation of the higher molecular weight carboxylicacylating agents preferably have up to about 500 carbon atoms permolecule. Preferred acylating agents (A)(I) are those containinghydrocarbyl groups of from about 20 to about 500 carbon atoms, morepreferably from about 30 to about 500 carbon atoms, more preferably fromabout 40 to about 500 carbon atoms, more preferably from about 50 toabout 500 carbon atoms.

The high-molecular weight polycarboxylic acylating agents (A)(I) mayalso be prepared by halogenating a high molecular weight hydrocarbonsuch as the above-described olefin polymers to produce a polyhalogenatedproduct, converting the polyhalogenated product to a polynitrile, andthen hydrolyzing the polynitrile. They may be prepared by oxidation of ahigh molecular weight polyhydric alcohol with potassium permanganate,nitric acid, or a similar oxidizing agent. Another method involves thereaction of an olefin or a polar-substituted hydrocarbon such as achloropolyisobutene with an unsaturated polycarboxylic acid such as2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of citricacid.

The polycarboxylic acid acylating agents (A)(I) can also be obtained byreacting chlorinated polycarboxylic acids, anhydrides, acyl halides, andthe like with ethylenically unsaturated hydrocarbons or ethylenicallyunsaturated substituted hydrocarbons such as the polyolefins andsubstituted polyolefins described hereinbefore in the manner describedin U.S. Pat. No. 3,340,281, this patent being incorporated herein byreference.

The high-molecular weight polycarboxylic acid anhydrides (A)(I) can beobtained by dehydrating the corresponding acids. Dehydration is readilyaccomplished by heating the acid to a temperature above about 70° C.,preferably in the presence of a dehydration agent, e.g., aceticanhydride. Cyclic anhydrides are usually obtained from polycarboxylicacids having acid groups separated by no more than three carbon atomssuch as substituted succinic or glutaric acid, whereas linear anhydridesare usually obtained from polycarboxylic acids having the acid groupsseparated by four or more carbon atoms.

The acid halides of the polycarboxylic acids can be prepared by thereaction of the acids or their anhydrides with a halogenating agent suchas phosphorus tribromide, phosphorus pentachloride, or thionyl chloride.

Hydrocarbyl-substituted succinic acids and the anhydride, acid halideand ester derivatives thereof are particularly preferred acylatingagents (A)(I). These acylating agents are preferably prepared byreacting maleic anhydride with a high molecular weight olefin or achlorinated hydrocarbon such as a chlorinated polyolefin. The reactioninvolves merely heating the two reactants at a temperature in the rangeof about 100° C. to about 300° C., preferably, about 100° C. to about200° C. The product from this reaction is a hydrocarbyl-substitutedsuccinic anhydride wherein the substituent is derived from the olefin orchlorinated hydrocarbon. The product may be hydrogenated to remove allor a portion of any ethylenically unsaturated covalent linkages bystandard hydrogenation procedures, if desired. Thehydrocarbyl-substituted succinic anhydrides may be hydrolyzed bytreatment with water or steam to the corresponding acid and either theanhydride or the acid may be converted to the corresponding acid halideor ester by reacting with a phosphorus halide, phenol or alcohol. Thehydrocarbyl-substituted succinic acids and anhydrides (A)(I) can berepresented by the formulae ##STR3## wherein R is the hydrocarbylsubstituent. Preferably R contains from about 20 to about 500 carbonatoms, more preferably from about 30 to about 500 carbon atoms, morepreferably from about 40 to about 500 carbon atoms, more preferably fromabout 50 to about 500 carbon atoms.

Although it is preferred that the acylating agent (A)(I) is an aliphaticpolycarboxylic acid, and more preferably a dicarboxylic acid, thecarboxylic acylating agent (A)(I) may also be an aromatic polycarboxylicacid or acid-producing compound. The aromatic acids are preferablyalkyl-substituted, dicarboxy-substituted benzene, naphthalene,anthracene, phenanthrene or like aromatic hydrocarbons. The alkyl groupsmay contain up to about 30 carbon atoms. The aromatic acid may alsocontain other substituents such as halo, hydroxy, lower alkoxy, etc.

Component (C)

Component (C) can be any compound having (i) two or more primary aminogroups, (ii) two or more secondary amino groups, (iii) at least oneprimary amino group and at least one secondary amino group, (iv) atleast two hydroxyl groups, or (v) at least one primary or secondaryamino group and at least one hydroxyl group. These incude polyamines,polyols and hydroxyamines.

(1) Polyamines Useful as Component (C)

The polyamines useful as component (C) are characterized by the presencewithin their structure of at least two --NH₂ groups, at least two >NHgroups, or at least one --NH₂ group and at least one >NH group.

These polyamines can be aliphatic, cycloaliphatic, aromatic orheterocyclic, including aliphatic-substituted aromatic,aliphatic-substituted cycloaliphatic, aliphatic-substitutedheterocyclic, cycloaliphatic-substituted aliphatic,cycloaliphatic-substituted aromatic, cycloaliphatic-substitutedheterocyclic, aromatic-substituted aliphatic, aromatic-substitutedcycloaliphatic, aromatic-substituted heterocyclic,heterocyclic-substituted aliphatic, heterocyclic-substitutedcycloaliphatic and heterocyclic-substituted aromatic amines. Theseamines may be saturated or unsaturated. If unsaturated, the amine ispreferably free from acetylenic unsaturation. These amines may alsocontain non-hydrocarbon substituents or groups as long as these groupsdo not significantly interfere with the reaction of such amines withreactants (A)(I) and (B)(I). Such non-hydrocarbon substituents or groupsinclude lower alkoxy, lower alkyl, mercapto, nitro, and interruptinggroups such as --O-- and --S-- (e.g., as in such groups as

    --CH.sub.2 CH.sub.2 --X--CH.sub.2 CH.sub.2 --

where X is --O-- or --S--).

The polyamines include aliphatic, cycloaliphatic and aromatic polyaminesanalogous to the aliphatic, cycloaliphatic and aromatic monoaminesdescribed below except for the presence within their structure of atleast one additional >NH or --NH₂ group.

Aliphatic monoamines include mono-aliphatic and di-aliphatic-substitutedamines wherein the aliphatic groups can be saturated or unsaturated andstraight or branched chain. Thus, they are primary or secondaryaliphatic amines. Such amines include, for example, mono- anddi-alkyl-substituted amines, mono- and dial-kenyl-substituted amines,and amines having one N-alkenyl substituent and one N-alkyl substituent,and the like. The total number of carbon atoms in these aliphaticmonoamines preferably does not exceed about 40 and usually does notexceed about 20 carbon atoms. Specific examples of such monoaminesinclude ethylamine, di-ethylamine, n-butylamine, di-n-butylamine,allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine,octadecylamine, and the like. Examples of cycloaliphatic-substitutedaliphatic amines, aromatic-substituted aliphatic amines, andheterocyclic-substituted aliphatic amines, include2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and3-(furylpropyl) amine.

Cycloaliphatic monoamines are those monoamines wherein there is onecycloaliphatic substituent attached directly to the amino nitrogenthrough a carbon atom in the cyclic ring structure. Examples ofcycloaliphatic monoamines include cyclohexylamines, cyclopentylamines,cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamines,dicyclohexylamines, and the like. Examples of aliphatic-substituted,aromatic-substituted, and heterocyclic-substituted cycloaliphaticmonoamines include propyl-substituted cyclohexylamines,phenyl-substituted cyclopentylamines and pyranyl-substitutedcyclohexylamine.

Aromatic monoamines include those monoamines wherein a carbon atom ofthe aromatic ring structure is attached directly to the amino nitrogen.The aromatic ring will usually be a mononuclear aromatic ring (i.e., onederived from benzene) but can include fused aromatic rings, especiallythose derived from naphthylene. Examples of aromatic monoamines includeaniline, di(paramethylphenyl) amine, naphthylamine, N-(n-butyl) aniline,and the like. Examples of aliphatic-substituted,cycloaliphatic-substituted, and heterocyclic-substituted aromaticmonoamines include para-ethoxyaniline, paradodecylamine,cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

Heterocyclic polyamines can also be used. As used herein, theterminology "heterocyclic polyamine" is intended to describe thoseheterocyclic amines containing at least two primary amino groups, atleast two secondary amino groups, or at least one of each, and at leastone nitrogen as a heteroatom in the heterocyclic ring. As long as thereis present in the heterocyclic polyamines at least two primary aminogroups, at least two secondary amino groups, or at least one of each,the hetero-N atom in the ring can be a tertiary amino nitrogen; that is,one that does not have hydrogen attached directly to the ring nitrogen.The hetero-N atom can be one of the secondary amino groups; that is, itcan be a ring nitrogen with hydrogen directly attached to it.Heterocyclic amines can be saturated or unsaturated and can containvarious substituents such as nitro, alkoxy, alkyl mercapto, alkyl,alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the totalnumber of carbon atoms in the substituents will not exceed about 20.Heterocyclic amines can contain heteroatoms other than nitrogen,especially oxygen and sulfur. Obviously they can contain more than onenitrogen heteroatom. The 5 - and 6-membered heterocyclic rings arepreferred.

Among the suitable heterocyclic polyamines are the aziridines,azetidines, azolidines, tetra- and di-hydro pyridines, pyrroles,indoles, piperadines, imidazoles, di- and tetra-hydroimidazoles,piperazines, isoindoles, purines, morpholines, thiomorpholines,N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,N-aminoalkylpiperazines, N,N'-di-aminoalkylpiperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro-derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Useful heterocyclic polyamines are the saturated 5- and6-membered heterocyclic polyamines containing only nitrogen, oxygenand/or sulfur in the hetero ring, especially the piperidines,piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.Usually the aminoalkyl substituents are substituted on a nitrogen atomforming part of the hetero ring. Specific examples of such heterocyclicamines include N-aminoethylpiperazine and N,N'-diaminoethylpiperazine.

Hydrazine and substituted-hydrazines can also be used. The substituentswhich may be present on the hydrazin include alkyl, alkenyl, aryl,aralkyl, alkaryl, and the like. Usually, the substituents are alkyl,especially lower alkyl, phenyl, and substituted phenyl such as loweralkoxy-substituted phenyl or lower alkyl-substituted phenyl. Specificexamples of substituted hydrazines are methylhydrazine,N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine,N-phenyl-N'-ethylhydrazine, N-(para-tolyl)-N'-(n-butyl)-hydrazine,N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)-N-methylhydrazine,N,N'-di-(para-chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine,and the like.

Another group of amines suitable for use in this invention are branchedpolyalkylene polyamines. The branched polyalkylene polyamines arepolyalkylene polyamines wherein the branched group is a side chaincontaining on the average at least one nitrogen-bonded aminoalkylene##STR4## group per nine amino units present on the main chain; forexample, 1-4 of such branched chains per nine units on the main chain,but preferably one side chain unit per nine main chain units. Thus,these polyamines contain at least three primary amino groups and atleast one tertiary amino group. These amines may be expressed by theformula: ##STR5## wherein R is an alkylene group such as ethylene,propylene, butylene and other homologs (both straight chained andbranched), etc., but preferably ethylene; and x, y and z are integers; xis in the range of from about 4 to about 24 or more, preferably fromabout 6 to about 18; y is in the range of from 1 to about 6 or more,preferably from 1 to about 3; and z is in the range of from zero toabout 6, preferably from zero to about 1. The x and y units may besequential, alternative, orderly or randomly distributed. A useful classof such polyamines includes those of the formula: ##STR6## wherein n isan integer in the range of from 1 to about 20 or more, preferably in therange of from 1 to about 3, and R is preferably ethylene, but may bepropylene, butylene, etc. (straight chained or branched). Usefulembodiments are represented by the formula: ##STR7## wherein n is aninteger in the range of 1 to about 3. The groups within the brackets maybe joined in a head-to-head or a head-to-tail fashion. U.S. Pat. Nos.3,200,106 and 3,259,578 are incorporated herein by reference for theirdisclosures relative to said polyamines.

Suitable polyamines also include polyoxyalkylene polyamines, e.g.,polyoxyalkylene diamines and polyoxyalkylene triamines, having averagemolecular weights ranging from about 200 to about 4000, preferably fromabout 400 to 2000. Examples of these polyoxyalkylene polyamines includethose amines represented by the formula:

    NH.sub.2 --Alkylene--O--Alkylene--.sub.m NH.sub.2

wherein m has a value of from about 3 to about 70, preferably from about10 to about 35.

    R--Alkylene--O--Alkylene--.sub.n NH.sub.2 ].sub.3-6

wherein n is a number in the range of from 1 to about 40, with theproviso that the sum of all of the n's is from about 3 to about 70 andgenerally from about 6 to about 35, and R is a polyvalent saturatedhydrocarbyl group of up to about 10 carbon atoms having a valence offrom about 3 to about 6. The alkylene groups may be straight or branchedchains and contain from 1 to about 7 carbon atoms, and usually from 1 toabout 4 carbon atoms. The various alkylene groups present within theabove formulae may be the same or different.

More specific examples of these polyamines include: ##STR8## wherein xhas a value of from about 3 to about 70, preferably from about 10 to 35;and ##STR9## wherein x+y+z have a total value ranging from about 3 toabout 30, preferably from about 5 to about 10.

Useful polyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to about 2000. Thepolyoxyalkylene polyamines are commercially available from the JeffersonChemical Company, Inc. under the trade name "Jeffamine". U.S. Pat. Nos.3,804,763 and 3,948,800 are incorporated herein by reference for theirdisclosure of such polyoxyalkylene polyamines.

Useful polyamines are the alkylene polyamines, including thepolyalkylene polyamines, as described in more detail hereafter. Thealkylene polyamines include those conforming to the formula: ##STR10##wherein n is from 1 to about 10, preferably from 1 to about 7; each Rand R' is independently a hydrogen atom, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, preferably up to about 100 carbon atoms, more preferably up toabout 50 carbon atoms, more preferably up to about 30 carbon atoms, withthe proviso that at least one of R and at least one of R' are hydrogen;and the "Alkylene" group has from about 1 to about 18 carbon atoms,preferably from 1 to about 4 carbon atoms, with the preferred Alkylenebeing ethylene or propylene. Useful alkylene polyamines are thosewherein each R and each R' is hydrogen with the ethylene polyamines, andmixtures of ethylene polyamines being particularly preferred. Suchalkylene polyamines include methylene polyamines, ethylene polyamines,butylene polyamines, propylene polyamines, pentylene polyamines,hexylene polyamines, heptylene polyamines, etc. The higher homologs ofsuch amines and related aminoalkyl-substituted piperazines are alsoincluded.

Alkylene polyamines that are useful include ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine, propylene diamine, trimethylene diamine, hexamethylenediamine, decamethylene diamine, octamethylene diamine,di(heptamethylene) triamine, tripropylene tetramine, tetraethylenepentamine, trimethylene diamine, pentaethylene hexamine,di(trimethylene) triamine, N-(2-aminoethyl) piperazine,1,4-bis(2-aminoethyl) piperazine, and the like. Higher homologs as areobtained by condensing two or more of the above-illustrated alkyleneamines are useful as amines in this invention as are mixtures of two ormore of any of the afore-described polyamines.

Ethylene polyamines, such as those mentioned above, are described indetail under the heading "Diamines and Higher Amines, Aliphatic" in TheEncyclopedia of Chemical Technology, Third Edition, Kirk-Othmer, Volume7, pp. 580-602, a Wiley-Interscience Publication, John Wiley and Sons,1979, these pages being incorporated herein by reference. Such compoundsare prepared most conveniently by the reaction of an alkylene chloridewith ammonia or by reaction of an ethylene imine with a ring-openingreagent such as ammonia, etc. These reactions result in the productionof the somewhat complex mixtures of alkylene polyamines, includingcyclic condensation products such as piperazines.

Alkoxylated alkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine)can be used. Such polyamines can be made by reacting alkylene amines(e.g., ethylenediamine) with one or more alkylene oxides (e.g., ethyleneoxide, octadecene oxide) of two to about 20 carbons. Similar alkyleneoxide-alkanol amine reaction products can also be used such as theproduts made by reacting the afore-described primary, secondary ortertiary alkanol amines with ethylene, propylene or higher epoxides in a1:1 or 1:2 molar ratio. Reactant ratios and temperatures for carryingout such reactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine,N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine,mono(hydroxypropyl)-substituted diethylene triamine,di(hydroxypropyl)-substituted tetraethylene pentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid polyamines arealso useful.

(2) Polyols Useful as Component (C)

The polyols or polyhydric alcohols useful as component (C) include thosecompounds of the general formula:

    R.sub.1 (OH).sub.m

wherein R₁ is a monovalent or polyvalent organic group joined to the--OH groups through carbon-to-oxygen bonds (that is, --COH wherein thecarbon is not part of a carbonyl group) and m is an integer of from 2 toabout 10, preferably 2 to about 6. These alcohols can be aliphatic,cycloaliphatic, aromatic, and heterocyclic, includingaliphatic-substituted cycloaliphatic alcohols, aliphatic-substitutedaromatic alcohols, aliphatic-substituted heterocyclic alcohols,cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted heterocyclic alcohols,heterocyclic-substituted aliphatic alcohols, heterocyclic-substitutedcycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols.Except for the polyoxyalkylene alcohols, the polyhydric alcoholscorresponding to the formula R₁ (OH)_(m) preferably contain not morethan about 40 carbon atoms, more preferably not more than about 20carbon atoms. The alcohols may contain non-hydrocarbon substituents orgroups which do not interfere with the reaction of the alcohols with thehydrocarbyl-substituted carboxylic acids or anhydrides of thisinvention. Such non-hydrocarbon substituents or groups include loweralkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as--O-- and --S-- (e.g., as in such groups as --CH₂ CH₂ --X--CH₂ CH₂ whereX is --O-- or --S--).

Useful polyoxyalkylene alcohols and derivatives thereof include thehydrocarbyl ethers and the carboxylic acid esters obtained by reactingthe alcohols with various carboxylic acids. Illustrative hydrocarbylgroups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc.,containing up to about 40 carbon atoms. Specific hydrocarbyl groupsinclude methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl,p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids usefulin preparing the ester derivatives are mono- or polycarboxylic acidssuch as acetic acid, valeric acid, lauric acid, stearic acid, succinicacid, and alkyl or alkenyl-substituted succinic acids wherein the alkylor alkenyl group contains up to about 20 carbon atoms. Members of thisclass of alcohols are commercially available from various sources; e.g.,PLURONICS, polyols available from Wyandotte Chemicals Corporation;POLYGLYCOL 112-2, a liquid triol derived from ethyleneoxide andpropylene-oxide available from Dow Chemical Co.; and TERGITOLS,dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS,polyalkylene glycols and various derivatives thereof, both availablefrom Union Carbide Corporation. However, the alcohols used must have anaverage of at least one free alcoholic hydroxyl group per molecule ofpolyoxyalkylene alcohol. For purposes of describing thesepolyoxyalkylene alcohols, an alcoholic hydroxyl group is one attached toa carbon atom that does not form part of an aromatic nucleus.

Alcohols useful in this invention also include alkylene glycols andpolyoxyalkylene alcohols such as polyoxyethylene alcohols,polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. Thesepolyoxyalkylene alcohols (sometimes called polyglycols) can contain upto about 150 oxyalkylene groups, with the alkylene group containing fromabout 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols aregenerally dihydric alcohols. That is, each end of the moleculeterminates with an OH group. In order for such polyoxyalkylene alcoholsto be useful, there must be at least two OH groups.

The polyhydric alcohols useful in this invention include polyhydroxyaromatic compounds. Polyhydric phenols and naphthols are usefulhydroxyaromatic compounds. These hydroxy-substituted aromatic compoundsmay contain other substituents in addition to the hydroxy substituentssuch as halo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like.Usually, the hydroxy aromatic compound will contain from 2 to about 4hydroxy groups. The aromatic hydroxy compounds are illustrated by thefollowing specific examples: resorcinol, catechol,p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol, phloroglucinol,hexylresorcinol, orcinol, etc.

The polyhydric alcohols preferably contain from 2 to about 10 hydroxygroups. They are illustrated, for example, by the alkylene glycols andpolyoxyalkylene glycols mentioned above such as ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropylene glycol, dibutylene glycol, tributylene glycol, andother alkylene glycols and polyoxyalkylene glycols in which the alkylenegroups contain from 2 to about 8 carbon atoms.

Other useful polyhydric alcohols include glycerol, monooleate ofglycerol, monostearate of glycerol, monomethyl ether of glycerol,pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methylester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol,2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol,1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars,starches, celluloses, and so forth likewise can be used. Thecarbohydrates may be exemplified by glucose, fructose, sucrose, rhamose,mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not allof which have been esterified with an aliphatic monocarboxylic acidhaving from about 8 to about 30 carbon atoms such as octanoic acid,oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oilacid are useful. Further specific examples of such partially esterifiedpolyhydric alcohols are the monooleate of sorbitol, distearate ofsorbitol, monooleate of glycerol, monostearate of glycerol,di-dodecanoate of erythritol, and the like.

Useful alcohols also include those polyhydric alcohols containing up toabout 12 carbon atoms, and especially those containing from about 3 toabout 10 carbon atoms. This class of alcohols includes glycerol,erythritol, pentaerythritol, dipentaerythritol, gluconic acid,glyceraldehyde, glucose, arabinose, 1,7-heptanediol, 2,4-heptanediol,1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol,2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid,2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol,digitalose, and the like. Aliphatic alcohols containing at least about 3hydroxyl groups and up to about 10 carbon atoms are useful.

Useful polyhydric alcohols are the polyhydric alkanols containing fromabout 3 to about 10 carbon atoms and particularly, those containingabout 3 to about 6 carbon atoms and having at least three hydroxylgroups. Such alcohols are exemplified by glycerol, erythritol,pentaerythritol, mannitol, sorbitol,2-hydroxymethyl-2-methyl-1,3-propanediol-(trimethylolethane),2-hydroxymethyl-2-ethyl-1,3-propanediol(trimethylopropane),1,2,4-hexanetriol, and the like.

(3) Hydroxyamines Useful as Component (C)

The hydroxyamines can be primary or secondary amines. They can also betertiary amines provided said tertiary amines also contain at least twohydroxyl groups. These hydroxyamines contain at least two >NH groups, atleast two --NH₂ groups, at least one --OH group and at least one >NH or--NH₂ group, or at least two --OH groups. The terms "hydroxyamine" and"aminoalcohol" describe the same class of compounds and, therefore, canbe used interchangeably.

The hydroxyamines can be primary or secondary alkanol amines or mixturesthereof. Such amines can be represented, respectfully, by the formulae:##STR11## wherein R is a hydrocarbyl group of one to about eight carbonatoms or hydroxyl-substituted hydrocarbyl group of two to about eightcarbon atoms and R' is a divalent hydrocarbyl group of about two toabout 18 carbon atoms. The group --R'--OH in such formulae representsthe hydroxyl-substituted hydrocarbyl group. R' can be an acyclic,alicyclic or aromatic group. Typically, R' is an acyclic straight orbranched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group. Typically, R is a loweralkyl group of up to seven carbon atoms.

The hydroxyamines can also be ether N-(hydroxy-substitutedhydrocarbyl)amines. These are hydroxyl-substituted poly(hydrocarbyloxy)analogs of the above-described primary and secondary alkanol amines(these analogs also include hydroxyl-substituted oxyalkylene analogs).Such N-(hydroxyl-substituted hydrocarbyl) amines can be convenientlyprepared by reaction of epoxides with afore-described amines and can berepresented by the formulae: ##STR12## wherein x is a number from about2 to about 15 and R and R' are as described above.

Polyamine analogs of these hydroxy amines, particularly alkoxylatedalkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine) can also beused. Such polyamines can be made by reacting alkylene amines (e.g.,ethylenediamine) with one or more alkylene oxides (e.g., ethylene oxide,octadecene oxide) of two to about 20 carbons. Similar alkyleneoxide-alkanol amine reaction products can also be used such as theproducts made by reacting the afore-described primary or secondaryalkanol amines with ethylene, propylene or higher epoxides in a 1:1 or1:2 molar ratio. Reactant ratios and temperatures for carrying out suchreactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine,N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine,mono(hydroxypropyl)-substituted diethylene triamine,di(hydroxypropyl)-substituted tetraethylene pentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid mono- orpolyamines are also useful.

Examples of the N-(hydroxyl-substituted hydrocarbyl) amines includemono-, di-, and triethanol amine, diethylethanol amine, di-(3-hydroxylpropyl) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine,N,N-di-(2-hydroxyl propyl) amine, N-(2-hydroxyl ethyl) morpholine andits thio analog, N-(2-hydroxyl ethyl) cyclohexyl amine, N-3-hydroxylcyclopentyl amine, o-, m- and p-aminophenol, N-(hydroxyl ethyl)piperazine, N,N'-di(hydroxyl ethyl) piperazine, and the like.

Further hydroxyamines are the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 by the general formula

    R.sub.a --NH.sub.2

wherein R_(a) is a monovalent organic group containing at least onealcoholic hydroxy group. The total number of carbon atoms in R_(a)preferably does not exceed about 20. Hydroxy-substituted aliphaticprimary amines containing a total of up to about 10 carbon atoms areuseful. The polyhydroxy-substituted alkanol primary amines wherein thereis only one amino group present (i.e., a primary amino group) having onealkyl substituent containing up to about 10 carbon atoms and up to about6 hydroxyl groups are useful. These alkanol primary amines correspond toR_(a) --NH₂ wherein R_(a) is a mono- or polyhydroxy-substituted alkylgroup. Specific examples of the hydroxy-substituted primary aminesinclude 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxypropyl)-N'-(beta-aminoethyl)-piperazine,tris(hydroxymethyl) amino methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine,beta-(beta-hydroxyethoxy)-ethyl amine, glucamine, glusoamine,4-amino-3-hydroxy-3-methyl-1-buten (which can be prepared according toprocedures known in the art by reacting isopreneoxide with ammonia),N-3-(aminopropyl)-4-(2-hydroxyethyl)-piperadine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)-1,3-diamino propane, 1,3-diamino-2-hydroxypropane,N-(beta-hydroxy ethoxyethyl)-ethylenediamine, trismethylolaminomethaneand the like. U.S. Pat. No. 3,576,743 is incorporated herein byreference.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkylsubstituents on the nitrogen atoms, are also useful. Usefulhydroxyalkyl-substituted alkylene polyamines include those in which thehydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less thaneight carbon atoms. Examples of such hydroxyalkyl-substituted polyaminesinclude N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)-piperazine,monohydroxypropyl-substituted diethylene triamine,dihydroxypropylsubstituted tetraethylene pentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained bycondensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia and condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater.

Components (A)(II) and (B)(II)

Components (A)(II) and (B)(II) can be the same or different, butpreferably are the same. The amines useful as component (A)(II) and(B)(II) in preparing the salt compositions of the invention includeammonia, and the primary amines, secondary amines and hydroxyaminesdiscussed above as being useful as component (C). In addition toammonia, the primary amines, secondary amines and hydroxyaminesdiscussed above, the amines useful as components (A)(II) and (B)(II)also include primary and secondary monoamines, and tertiary mono- andpolyamines. The primary and secondary monoamines that are useful ascomponents (A)(II) and (B)(II) are described above under the sub-title"(1) Polyamines Useful as Component (C)" as being analogues of thepolyamines described above. These primary and secondary monoaminesinclude the aliphatic, cycloaliphatic and aromatic monoamines discussedabove. The tertiary amines are analogous to the primary amines,secondary amines and hydroxyamines discussed above with the exceptionthat they can be either monoamines or polyamines and the hydrogen atomsin the H--N< or --NH₂ groups are replaced by hydrocarbyl groups.

The tertiary amines can be aliphatic, cycloaliphatic, aromatic orheterocyclic, including aliphatic-substituted aromatic,aliphatic-substituted cycloaliphatic, aliphatic-substitutedheterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphaticsubstituted aromatic, cycloaliphatic-substituted heterocyclic,aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic,aromatic-substituted heterocyclic, heterocyclic-substituted aliphatic,heterocyclic-substituted cycloaliphatic and heterocyclic-substitutedaromatic amines. These tertiary amines may be saturated or unsaturated.If unsaturated, the amine is preferably free from acetylenicunsaturation. The tertiary amines may also contain non-hydrocarbonsubstituents or groups as long as these groups do not significantlyinterfere with the reaction of component (B) with component (A). Suchnon-hydrocarbon substituents or groups include lower alkoxy, loweralkyl, mercapto, nitro, and interrupting groups such as --O-- and --S--(e.g., as in such groups as --CH₂ CH₂ --X--CH₂ CH₂ -- where X is --O--or --S--).

The monoamines can be represented by the formula ##STR13## wherein R',R² and R³ are the same or different hydrocarbyl groups. Preferably, R',R² and R³ are independently hydrocarbyl groups of from 1 to about 20carbon atoms.

Examples of useful tertiary amines include trimethyl amine, triethylamine, tripropyl amine, tributyl amine, monomethyldiethylamine,monoethyldimethyl amine, dimethylpropyl amine, dimethylbutyl amine,dimethylpentyl amine, dimethylhexyl amine, dimethylheptyl amine,dimethyloctyl amine, dimethylnonyl amine, dimethyldecyl amine,dimethylphenyl amine, N,N-dioctyl-1-octanamine,N,N-didodecyl-1-dodecanamine tricoco amine, trihydrogenated-tallowamine, N-methyl-dihydrogenated tallow amine,N,N-dimethyl-1-dodecanamine, N,N-dimethyl-1-tetradecanamine,N,N-dimethyl-1-hexadecanamine, N,N-dimethyl- 1-octadecanamine,N,N-dimethylcocoamine, N,N-dimethylsoyaamine, N,N-dimethylhydrogenatedtallow amine, etc.

Useful tertiary alkanol amines are represented by the formula ##STR14##wherein each R is independently a hydrocarbyl group of one to abouteight carbon atoms or hydroxyl-substituted hydrocarbyl group of two toabout eight carbon atoms and R' is a divalent hydrocarbyl group of abouttwo to about 18 carbon atoms. The group --R'--OH in such formularepresents the hydroxyl-substituted hydrocarbyl group. R'an be anacyclic, alicyclic or aromatic group. Typically, R' is an acyclicstraight or branched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group. Where two R groups arepresent in the same molecule they can be joined by a directcarbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen orsulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples ofsuch heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines,-thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and thelike. Typically, however, each R is a lower alkyl group of up to sevencarbon atoms. The hydroxyamines can also be an etherN-(hydroxy-substituted hydrocarbyl)amine. These are hydroxyl-substitutedpoly(hydrocarbyloxy) analogs of the above-described hydroxy amines(these analogs also include hydroxyl-substituted oxyalkylene analogs).Such N-(hydroxyl-substituted hydrocarbyl) amines can be convenientlyprepared by reaction of epoxides with afore-described amines and can berepresented by the formula: ##STR15## wherein x is a number from about 2to about 15 and R and R' are as described above.

Useful polyamines include the alkylene polyamines discussed above aswell as alkylene polyamines with only one or no hydrogens attached tothe nitrogen atoms. Thus, the alkylene polyamines useful as components(A)(II) and (B)(II) include those conforming to the formula: ##STR16##wherein n is from 1 to about 10, preferably from 1 to about 7; each R isindependently a hydrogen atom, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, preferably up to about 100 carbon atoms, more preferably up toabout 50 carbon atoms, more preferably up to about 30 carbon atoms; andthe "Alkylene" group has from about 1 to about 18 carbon atoms,preferably from 1 to about 4 carbon atoms, with the preferred Alkylenebeing ethylene or propylene.

The alkali and alkaline earth metals that are useful as components(A)(II) and (B)(II) can be any alkali or alkaline earth metal. Thealkali metals are preferred. Sodium and potassium are particularlypreferred. The alkali and alkaline earth metal compounds that are usefulinclude, for example, the oxides, hydroxides and carbonates. Sodiumhydroxide and potassium hydroxide are particularly preferred.

Formation of the Salt Compositions

The salt compositions of the invention can be prepared by initiallyreacting the acylating agents (A)(I) and (B)(I) with component (C) toform an intermediate, and thereafter reacting said intermediate withcomponents (A)(II) and (B)(II) to form the desired salt. An alternativemethod of preparing these salt compositions involves reacting components(A)(I) and (A)(II) with each other to form a first salt moiety,separately reacting components (B)(I) and (B)(II) with each otherto forma second salt moiety, then reacting a mixture of these two salt moietieswith component (C).

The ratio of reactants utilized in the preparation of the inventive saltcompositions may be varied over a wide range. Generally, for eachequivalent of each of the acylating agents (A)(I) and (B)(I), at leastabout one equivalent of component (C) is used. From about 0.1 to about 2equivalents or more of components (A)(II) and (B)(II) are used for eachequivalent of components (A)(I) and (B)(I), respectively. The upperlimit of component (C) is about 2 equivalents of component (C) for eachequivalent of component (A)(I), and about two equivalents of component(C) for each equivalent of component (B)(I). Generally the ratio ofequivalents of components (A)(I) to (B)(I) is about 0.5 to about 2, withabout 1:1 being preferred. Preferred amounts of the reactants are about2 equivalents of the component (C) and from about 0.1 to about 2equivalents of each of components (A)(II) and (B)(II) for eachequivalent of each of components (A)(I) and (B)(I).

The number of equivalents of the acylating agents (A)(I) and (B)(I)depends on the total number of carboxylic functions present in each. Indetermining the number of equivalents for each of the acylating agents(A)(I) and (B)(I), those carboxyl functions which are not capable ofreacting as a carboxylic acid acylating agent are excluded. In general,however, there is one equivalent of acylating agent (A)(I) and (B)(I)for each carboxy group in these acylating agents. For example, therewould be two equivalents in an anhydride derived from the reaction ofone mole of olefin polymer and one mole of maleic anhydride.Conventional techniques are readily available for determining the numberof carboxyl functions (e.g., acid number, saponification number) and,thus, the number of equivalents of each of the acylating agents (A)(I)and (B)(I) can be readily determined by one skilled in the art.

An equivalent weight of a polyamine is the molecular weight of thepolyamine divided by the total number of nitrogens present in themolecule. If the polyamine is to be used as component (C), tertiaryamino groups are not counted. On the other hand, if the polyamine is tobe used as component (A)(II) or (B)(II), tertiary amino groups arecounted. Thus, ethylene diamine has an equivalent weight equal toone-half of its molecular weight; diethylene triamine has an equivalentweight equal to one-third its molecular weight. The equivalent weight ofa commercially available mixture of polyalkylene polyamine can bedetermined by dividing the atomic weight of nitrogen (14) by the % Ncontained in the polyamine; thus, a polyamine mixture having a % N of 34would have an equivalent weight of 41.2. An equivalent weight of ammoniaor a monoamine is its molecular weight.

An equivalent weight of polyhydric alcohol is its molecular weightdivided by the total number of hydroxyl groups present in the molecule.Thus, an equivalent weight of ethylene glycol is one-half its molecularweight.

An equivalent weight of a hydroxyamine which is to be used as component(C) is its molecular weight divided by the total number of --OH, >NH and--NH₂ groups present in the molecule. Thus, dimethylethanolamine whenused as component (C) has an equivalent weight equal to its molecularweight; ethanolamine has an equivalent weight equal to one-half itsmolecular weight. On the other hand, if the hydroxyamine is to be usedas components (A)(II) or (B)(II), an equivalent weight thereof would beits molecular weight divided by the total number of nitrogen groupspresent in the molecule. Thus, dimethylethanolamine, when used ascomponent (A)(II) or (B)(II), would have an equivalent weight equal toits molecular weight; ethanolamine would also have an equivalent weightequal to its molecular weight.

An equivalent weight of an alkali or alkaline earth metal is itsmolecular weight. An equivalent weight of an alkali or alkaline earthmetal compound is its molecular weight divided by the number of alkalior alkaline earth metal atoms present in the molecule.

The acylating agents (A)(I) and (B)(I) can be reacted with component (C)according to conventional ester- and/or amide-forming techniques. Thisnormally involves heating acylating agents (A)(I) and (B)(I) withcomponent (C), optionally in the presence of a normally liquid,substantially inert, organic liquid solvent/diluent. Temperatures of atleast about 30° C. up to the decomposition temperature of the reactioncomponent and/or product having the lowest such temperature can be used.This temperature is preferably in the range of about 50° C. to about130° C., mre preferably about 80° C. to about 100° C. when the acylatingagents (A)(I) and (B)(I) are anhydrides. On the other hand, when theacylating agents (A)(I) and (B)(I) are acids, this temperature ispreferably in the range of about 100° C. to about 300° C. withtemperatures in the range of about 125° C. to about 250° C. often beingemployed.

The reactions between components (A)(I) and (B)(I), and (A)(II) and(B)(II) are carried out under salt forming conditions using conventionaltechniques. Typically, components (A)(I) and (A)(II), and (B)(I) and(B)(II) are mixed together and heated to a temperature in the range ofabout 20° C. up to the decomposition temperature of the reactioncomponent and/or product having the lowest such temperature, preferablyabout 50° C. to about 130° C., more preferably about 80° C. to about110° C.; optionally, in the presence of a normally liquid, substantiallyinert organic liquid solvent/diluent, until the desired product hasformed.

The product of the reaction between components (A)(I) and (B)(I), and(A)(II) and (B)(II), respectively, must contain at least some saltlinkage to permit said product to be effective as an emulsifier inaccordance with the invention. Preferably at least about 10%, morepreferably at least about 30%, more preferably at least about 50%, morepreferably at least about 70%, and advantageously up to about 100% ofcomponents (A)(II) and (B)(II) that react with the acylating agents(A)(I) and (B)(I), respectively, form a salt linkage.

The following examples illustrate the preparation of the saltcompositions of this invention. Unless otherwise indicated, in thefollowing examples and elsewhere in the specification and claims, allparts and percentages are by weight, and all temperatures are in degreescentigrade.

EXAMPLE 1

1120 parts of polyisobutylene (number average molecular weight=950)substituted succinic anhydride and 325 parts of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₆ alpha-olefin and one mole of maleic anhydride are heated to atemperature of 93° C. with stirring and maintained at that temperaturefor one hour. 62 parts of ethylene glycol are added to the mixture. Themixture is maintained at a temperature of 93°-105° C. for 2 hours. 178parts of dimethylethanolamine are added to the mixture over a period of0.5 hour. The mixture is maintained at 93°-104° C. for 2.5 hours thencooled to 70° C. to provide the desired product.

EXAMPLE 2

1370 parts of polyisobutylene (number average molecular weight 1200),substituted succinic anhydride, 260 parts of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₂ alpha-olefin and one mole of maleic anhydride, and 104 parts ofneopentyl glycol are reacted under ester-forming conditions to form anintermediate product. 234 parts of diethylethanolamine are reacted withthe intermediate product under salt-forming conditions to form a desiredsalt composition.

EXAMPLE 3

1120 parts of the polyisobutylene substituted succinic anhydrideidentified in Example 1, 260 parts of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₂ alpha-olefin and one mole of maleic anhydride, and 104 parts ofneopentyl glycol are reacted under ester-forming conditions to form anintermediate product. 234 parts of diethylethanolamine are reacted withthe intermediate product under salt-forming conditions to form a desiredsalt composition.

EXAMPLE 4

1370 parts of the polyisobutylene substituted succinic anhydrideidentified in Example 2, 325 parts of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₆ alpha-olefin and one mole of maleic anhydride, and 104 parts ofneopentyl glycol are reacted under ester-forming conditions to form anintermediate product. 234 parts of diethylethanolamine are reacted withthe intermediate product under salt-forming conditions to form a desiredsalt composition.

EXAMPLE 5

1120 parts of the polyisobutylene substituted succinic anhydrideidentified in Example 1, 325 parts of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₆ alpha-olefin and one mole of maleic anhydride, and 75 parts ofN-methylethanolamine are reacted under ester-amide-forming conditions toform an intermediate product. 298 parts of triethanolamine are reactedwith the intermediate product under salt-forming conditions to form adesired salt composition.

EXAMPLE 6

1120 parts of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, 325 parts of a low-molecular weighthydrocarbyl-substituted succinic anhydride derived from a C₁₆alpha-olefin and maleic anhydride, and 75 parts of N-methylethanolamineare reacted under ester-amide forming conditions to form an intermediateproduct. 179 parts of triethylamine are reacted with the intermediateproduct under salt-forming conditions to form a desired saltcomposition.

EXAMPLE 7

1120 parts of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, 325 parts of a low-molecular weighthydrocarbyl-substituted succinic anhydride derived from a C₁₆alpha-olefin and maleic anhydride, and 106 parts of diethylene glycolare reacted under ester-forming conditions to form an intermediateproduct. 234 parts of diethylethanolamine are reacted with theintermediate product under salt-forming conditions to form a desiredsalt composition.

EXAMPLE 8

1120 parts of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, 325 parts of a low-molecular weighthydrocarbyl-substituted succinic anhydride derived from a C₁₆alpha-olefin and maleic anhydride, and 75 parts of propylene glycol arereacted under ester-forming conditions to form an intermediate product.210 parts of diethanolamine are reacted with the intermediate productunder salt-forming conditions to form a desired salt composition.

EXAMPLE 9

1370 parts of the polyisobutylene-substituted succinic anhydrideidentified in Example 2, 325 parts of a low-molecular weighthydrocarbyl-substituted succinic anhydride derived from a C₁₆alpha-olefin and maleic anhydride, and 118 parts of hexylene glycol arereacted under ester-forming conditions to form an intermediate product.179 parts of triethylamine are reacted with the intermediate productunder salt-forming conditions to form a desired salt composition.

EXAMPLE 10

1120 parts of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, 260 parts of a low-molecular weighthydrocarbyl-substituted succinic anhydride derived from a C₁₂alpha-olefin and maleic anhydride, and 104 parts of pentanediol arereacted under ester-forming conditions to form an intermediate product.298 parts of triethanolamine are reacted with the intermediate productunder salt-forming conditions to form a desired salt composition.

EXAMPLE 11

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, two equivalents of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₆₋₁₈ alpha-olefin fraction and one mole of maleic anhydride, and twoequivalents of ethylene diamine are reacted under amide-formingconditions to form an intermediate product. Two equivalents of NaOH arereacted with the intermediate product under salt-forming conditions toform a desired salt composition.

EXAMPLE 12

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, two equivalents of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₂ alpha-olefin and one mole of maleic anhydride, and two equivalentsof N-methylethanolamine are reacted under ester-amide-forming conditionsto form an intermediate product. Two equivalents of calcium hydroxideare reacted with the intermediate product under salt-forming conditionsto form a desired salt composition.

EXAMPLE 13

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, two equivalents of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of a C₈alpha-olefin and one mole of maleic anhydride, and two equivalents ofethylene diamine are reacted under amide-forming conditions to form anintermediate product. Two equivalents of ammonia are reacted with theintermediate product under salt-forming conditions to form a desiredsalt composition.

EXAMPLE 14

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, two equivalents of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₂₋₁₆ alpha-olefin fraction and one mole of maleic anhydride, and twoequivalents of ethylene glycol are reacted under ester-formingconditions to form an intermediate product. Two equivalents of potassiumcarbonate are reacted with the intermediate product under saltformingconditions to form a desired salt composition.

EXAMPLE 15

Two equivalents of a C₂₀ hydrocarbyl-substituted succinic anhydride, twoequivalents of a low molecular weight hydrocarbyl-substituted succinicanhydride derived from one mole of a C₁₈ alpha-olefin and one mole ofmaleic anhydride, and two equivalents of ethylene diamine are reactedunder amide-forming conditions to form an intermediate product. Twoequivalents of dimethylethanolamine are reacted with the intermediateproduct under salt-forming conditions to form a desired saltcomposition.

EXAMPLE 16

Two equivalents of a C₅₀₀ -hydrocarbyl-substituted succinic anhydride,two equivalents of a low molecular weight hydrocarbyl-substitutedsuccinic anhydride derived from one mole of a C₈ alpha-olefin and onemole of maleic anhydride, and two equivalents of ethylene glycol arereacted under ester-forming conditions to form an intermediate product.Two equivalents of ammonia are reacted with the intermediate productunder salt-forming conditions to form a desired salt composition.

EXAMPLE 17

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, two equivalents of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₆ alpha-olefin and one mole of maleic anhydride, and two equivalentsof ethylene glycol are reacted under ester-forming conditions to form anintermediate product. Two equialents of sodium hydroxide are reactedwith the intermediate product under salt-forming conditions to form adesired salt composition.

EXAMPLE 18

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, two equivalents of a low molecular weighthydrocarbyl-substituted succinic anhydride derived from one mole of aC₁₆₋₁₈ alpha-olefin fraction and one mole of maleic anhydride, and twoequivalents of ethylene diamine are reacted under amide-formingconditions to form an intermediate product. Two equivalents ofmorpholine are reacted with the intermediate product under salt-formingconditions to form a desired salt composition.

EXAMPLE 19

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1, two equivalents of maleic anhydride, and twoequivalents of ethylene glycol are reacted under ester-formingconditions to form an intermediate product. Two equivalents ofdimethylethanolamine are reacted with the intermediate product undersalt-forming conditions to form a desired salt composition.

Explosive Compositions

The explosive compositions of the invention are water-in-oil emulsionswhich, in one embodiment, are cap-sensitive water-in-oil explosiveemulsions. These explosive emulsions employ the salt compositions of theinvention as emulsifiers. The inventive explosive emulsions comprise adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least onecarbonaceous fuel, and an emulsifying amount of at least one of the saltcompositions of the invention.

The continuous organic phase is preferably present at a level of atleast about 2% by weight, more preferably in the range of from about 2%to about 15% by weight, more preferably in the range of from about 3.5%to about 8% by weight based on the total weight of explosive emulsion.The discontinuous oxidizer phase is preferably present at a level of atleast about 85% by weight, more preferably at a level in the range offrom about 85% to about 98% by weight, more preferably from about 92% toabout 96.5% by weight based on the total weight of said explosiveemulsion. The salt compositions of the invention are preferably presentat a level in the range of from about 4% to about 40% by weight, morepreferably from about 12% to about 20% by weight based on the totalweight of the organic phase. The oxygen-supplying component ispreferably present at a level in the range of from about 70% to about95% by weight, more preferably from about 85% to about 92% by weight,more preferably from about 87% to about 90% by weight based on the totalweight of the oxidizer phase. The water is preferably present at a levelin the range of about 5% to about 30% by weight, more preferably about8% to about 15% by weight, more preferably about 10% to about 13% byweight based on the weight of the oxidizer phase.

The carbonaceous fuel that is useful in the explosive emulsions of theinvention can include most hydrocarbons, for example, paraffinic,olefinic, naphthenic, aromatic, saturated or unsaturated hydrocarbons,and is typically in the form of an oil or a wax or a mixture thereof. Ingeneral, the carbonaceous fuel is a water-immiscible, emulsifiablehydrocarbon that is either liquid or liquefiable at a temperature of upto about 95° C., and preferably between about 40° C. and about 75° C..Oils from a variety of sources, including natural and synthetic oils andmixtures thereof can be used as the carbonaceous fuel.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as solvent-refined or acid-refined mineral oils of theparaffinic, naphthenic, or mixed paraffin-naphthenic types. Oils derivedfrom coal or shale are also useful. Synthetic oils include hydrocarbonoils and halo-substituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);alkyl benzenes (e.g., dodecylbenzenes, tetradecylbenzenes,dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.); polyphenyls (e.g.,biphenyls, terphenyls, alkylated polyphenyls, etc.); and the like.

Another suitable class of synthetic oils that can be used comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid,fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols(e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexylalcohol, ethylene glycol, diethylene glycol monoether, propylene glycol,pentaerythritol, etc.). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)-sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles of2-ethyl-hexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another class ofuseful oils. These include tetraethyl-silicate, tetraisopropylsilicate,tetra-(2-ethylhexyl)-silicate, tetra-(4-methylhexyl)-silicate,tetr(p-tert-butylphenyl)-silicate,hexyl-(4-methyl-2-pentoxy)-di-siloxane, poly(methyl)siloxanes,poly-(methylphenyl)-siloxanes, etc. Other useful synthetic oils includeliquid esters of phosphorus-containing acid (e.g., tricresyl phosphate,trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.),polymeric tetrahydrofurans, and the like.

Unrefined, refined and rerefined oils (and mixtures of each with eachother) of the type disclosed hereinabove can be used. Unrefined oils arethose obtained directly from a natural or synthetic source withoutfurther purification treatment. For example, a shale oil obtaineddirectly from a retorting operation, a petroleum oil obtained directlyfrom distillation or ester oil obtained directly from an esterificationprocess and used without further treatment would be an unrefined oil.Refined oils are similar to the unrefined oils except that they havebeen further treated in one or more purification steps to improve one ormore properties. Many such purification techniques are known to those ofskill in the art such as solvent extraction, distillation, acid or baseextraction, filtration, percolation, etc. Rerefined oils are obtained byprocesses similar to those used to obtain refined oils applied torefined oils which have been already used in service. Such rerefinedoils are also known as reclaimed or reprocessed oils and often areadditionally processed by techniques directed toward removal of spentadditives and oil breakdown products.

Examples of useful oils include a white mineral oil available from WitcoChemical Company under the trade designation KAYDOL; a white mineral oilavailable from Shell under the trade designation ONDINA; and a mineraloil available from Pennzoil under the trade designation N-750-HT.

The carbonaceous fuel can be any wax having melting point of at leastabout 25° C., such as petrolatum wax, microcrystalline wax, and paraffinwax, mineral waxes such as ozocerite and montan wax, animal waxes suchas spermacetic wax, and insect waxes such as beeswax and Chinese wax.Useful waxes include waxes identified by the trade designation MOBILWAX57 which is available from Mobil Oil Corporation; D02764 which is ablended wax available from Astor Chemical Ltd.; and VYBAR which isavailable from Petrolite Corporation. Preferred waxes are blends ofmicrocrystalline waxes and paraffin.

In one embodiment, the carbonaceous fuel includes a combination of a waxand an oil. In this embodiment, the wax content is at least about 25%and preferably ranges from about 25% to about 90% by weight of theorganic phase, and the oil content is at least about 10% and preferablyranges from about 10% to about 75% by weight of the organic phase. Thesemixtures are particularly suitable for use in cap-sensitive explosiveemulsions.

While its presence is not necessary, the explosive emulsions can alsocontain up to about 15% by weight of an auxiliary fuel, such asaluminum, aluminum alloys, magnesium, and the like. Particulate aluminumis a preferred auxiliary fuel.

The oxygen-supplying component is preferably at least one inorganicoxidizer salt such as ammonium, alkali or alkaline earth metal nitrate,chlorate or perchlorate. Examples inlcude ammonium nitrate, sodiumnitrate, calcium nitrate, ammonium chlorate, sodium perchlorate andammonium perchlorate. Ammonium nitrate is especially preferred. Mixturesof ammonium nitrate and sodium or calcium nitrate are also preferred. Inone embodiment, inorganic oxidizer salt comprises principally ammoniumnitrate, although up to about 25% by weight of the oxidizer phase cancomprise either another inorganic nitrate (e.g., alkali or alkalineearth metal nitrate) or an inorganic perchlorate (e.g., ammoniumperchlorate or an alkali or alkaline earth metal perchlorate) or amixture thereof.

In one embodiment of the invention, closedcell, void-containingmaterials are used as sensitizing components. The term "closed-cell,void-containing material" is used herein to mean any particulatematerial which comprises closed cell, hollow cavities. Each particle ofthe material can contain one or more closed cells, and the cells cancontain a gas, such as air, or can be evacuated or partially evacuated.In one embodiment of the invention, sufficient closed cell voidcontaining material is used to yield a density in the resulting emulsionof from about 0.8 to about 1.35 g/cc, more preferably about 0.9 to about1.3 g/cc, more preferably about 1.1 to about 1.3 g/cc. In general, theemulsions of the subject invention can contain up to about 15% byweight, preferably from about 0.25% to about 15% by weight of the closedcell void containing material. Preferred closed cell void containingmaterials are discrete glass spheres having a particle size within therange of about 10 to about 175 microns. In general, the bulk density ofsuch particles can be within the range of about 0.1 to about 0.4 g/cc.Useful glass microbubbles which can be used are the microbubbles sold by3M Company and which have a particle size distribution in the range offrom about 10 to about 160 microns and a nominal size in the range ofabout 60 to 70 microns, and densities in the range of from about 0.1 toabout 0.4 g/cc.; these include microbubbles distributed under the tradedesignation B15/250. Other useful glass microbubbles are sold under thetrade designation of ECCOSPHERES by Emerson & Cumming, Inc., andgenerally have a particle size range from about 44 to about 175 micronsand a bulk density of about 0.15 to about 0.4 g/cc. Other suitablemicrobubbles include the inorganic microspheres sold under the tradedesignation of Q-CEL by Philadelphia Quartz Company. The closed cellvoid containing material can be made of inert or reducing materials. Forexample, phenol-formaldehyde microbubbles can be utilized within thescope of this invention. If the phenol-formaldehyde microbubbles areutilized, the microbubbles themselves are a fuel component for theexplosive and their fuel value should be taken into consideration whendesigning a water-in-oil emulsion explosive composition. Another closedcell void containing material which can be used within the scope of thesubject invention is the saran microspheres sold by Dow ChemicalCompany. The saran microspheres have a diameter of about 30 microns anda particle density of about 0.032 g/cc. Because of the low bulk densityof the saran microspheres, it is preferred that only from about 0.25 toabout 1% by weight thereof be used in the water-in-oil emulsions of thesubject invention.

Gas bubbles which are generated in-situ by adding to the composition anddistributing therein a gas-generating material such as, for example, anaqueous solution of sodium nitrite, can also be used can be used tosensitize the explosive emulsions. Other suitable sensitizing componentswhich may be employed alone or in addition to the foregoing includeinsoluble particulate solid self-explosives such as, for example,grained or flaked TNT, DNT, RDX and the like and water-soluble and/orhydrocarbon-soluble organic sensitizers such as, for example, aminenitrates, alkanolamine nitrates, hydroxyalkyl nitrates, and the like.The explosive emulsions of the present invention may be formulated for awide range of applications. Any combination of sensitizing componentsmay be selected in order to provide an explosive composition ofvirtually any desired density, weight-strength or critical diameter. Thequantity of solid self-explosive ingredients and of water-soluble and/orhydrocarbon-soluble organic sensitizers may comprise up to about 40% byweight of the total explosive composition. The volume of the occludedgas component may comprise up to about 50% of the volume of the totalexplosive composition.

Optional additional materials may be incorporated in the explosiveemulsions of the invention in order to further improve sensitivity,density, strength, rheology and cost of the final explosive. Typical ofmaterials found useful as optional additives include, for example,particulate non-metal fuels such as sulfur, gilsonite and the like,particulate inert materials such as sodium chloride, barium sulphate andthe like, water phase or hydrocarbon phase thickeners such as guar gum,polyacrylamide, carboxymethyl or ethyl cellulose, biopolymers, starches,elastomeric materials, and the like, crosslinkers for the thickenerssuch as potassium pyroantimonate and the like, buffers or pH controllerssuch as sodium borate, zinc nitrate and the like, crystals habitmodifiers such as alkyl naphthalene sodium sulphonate and the like,liquid phase extenders such as formamide, ethylene glycol and the likeand bulking agents and additives of common use in the explosives art.The quantities of optional additional materials used may comprise up toabout 50% by weight of the total explosive emulsion.

The general criteria for cap-sensitivity is that the explosive besensitive to a No. 8 blasting cap at a cartridge diameter of 1.25 inchunder normal temperature conditions. The cap-sensitive explosiveemulsions of the present invention are shelf stable, which means theyexhibit shelf stability of at least six months and typically one year ormore.

A preferred method for making the explosive emulsions of the inventioncomprises the steps of (1) mixing water, inorganic oxidizer salts (e.g.,ammonium nitrate) and, in certain cases, some of the supplementalwater-soluble compounds, in a first premix, (2) mixing the carbonaceousfuel, the emulsifying salt compositions of the invention and any otheroptional oil-soluble compounds, in a second premix and (3) adding thefirst premix to the second premix in a suitable mixing apparatus, toform a water-in-oil emulsion. The first premix is heated until all thesalts are completely dissolved and the solution may be filtered ifneeded in order to remove any insoluble residue. The second premix isalso heated to liquefy the ingredients. Any type of apparatus capable ofeither low or high shear mixing can be used to prepare thesewater-in-oil emulsions. Closed-cell void containing materials,gas-generating materials, solid self-explosive ingredients such asparticulate TNT, solid fuels such as aluminum or sulfur, inert materialssuch as barytes or sodium chloride, undissolved solid oxidizer salts andother optional materials, if employed, are added to the emulsion andsimply blended until homogeneously dispersed throughout the composition.

The water-in-oil explosive emulsions of the invention can also beprepared by adding the second premix liquefied organic solution phase tothe first premix hot aqueous solution phase with sufficient stirring toinvert the phases. However, this method usually requires substantiallymore energy to obtain the desired dispersion than does the preferredreverse procedure. Alternatively, these water-in-oil explosive emulsionsare particularly adaptable to preparation by a continuous mixing processwhere the two separately prepared liquid phases are pumped through amixing device wherein they are combined and emulsified.

The salt compositions of this invention can be added directly to theinventive explosive emulsions. They can also be diluted with asubstantially inert, normally liquid organic diluent such as mineraloil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate. These concentrates usually contain from about 10% to about90% by weight of the salt composition of this invention and may contain,in addition, one or more other additives known in the art or describedhereinabove.

An advantage of the present invention is that by using the saltcompositions of the present invention as emulsifiers, explosiveemulsions can be provided in gelatinous or semi-gelatinous forms thatare dry to the touch and cuttable. These are important characteristicswhen using these explosive emulsions in the preparation of cap-sensitiveexplosive emulsions, particularly when such cap-sensitive explosiveemulsions are used in the manufacture of explosive cartridges,especially small diameter (i.e., diameters of about 1.25 inches orsmaller) cartridges.

Explosive cartridges within the scope of this invention can be madeusing techniques well known in the art. The cap-sensitive explosiveemulsions of the invention are particularly suitable for makingcartridges on cartridging machines such as the type available fromNiepmann under the trade designation ROLLEX.

The following Examples A-G are illustrative of cap-sensitivewater-in-oil explosive emulsions within the scope of the invention.Examples A-E, which are identified in Table I below, are prepared asfollows. The organic phase is prepared using the wax and oil indicatedin Table I and the product of Example 1. The oxidizer phase contains78.5% NH₄ NO₃, 10.7% NaNO₃, and 10.8% H₂ O. The weight ratio of theoxidizer phase to the organic phase is 95/5. The organic phase is meltedat 90° C.. The oxidizer phase is heated to 104° C.. The oxidizer phaseis added to the organic phase with stirring using a Sunbeam Mixmastermixer at 50-100% on the variac for one minute. The emulsions are mixedor "worked" an additional six minutes in the Sunbeam Mixmaster mixer at100% on the variac. The viscosity of each emulsion and initial emulsiontemperatures are indicated in Table I. A sample of each emulsion isstored at 49° C. for 4 days and then at 70° C. for 2 days. After thattime the emulsions are removed and stored at room temperature. Thestability of each emulsion is observed overtime and reported in Table I.The penetration of the samples is measured using a 159 gram cone andapparatus.

                  TABLE I                                                         ______________________________________                                                   A     B       C       D     E                                      ______________________________________                                        Product of Ex. 1,                                                                          20      20      20    15    25                                   (% of organic phase)                                                          Mineral oil, 20      32      40    20    15                                   (% of organic phase)                                                          50:50 blend of micro-                                                                      60      48      40    65    60                                   crystalline wax and                                                           paraffin wax,                                                                 (% of organic phase)                                                          Initial Viscosity                                                                          115/    125/    120/  95/   160/                                 (cPs × 10.sup.3 /°F.)                                                         170     162     166   170   166                                  Avg. Penetration at                                                                        8.95    10.7    11.5  8.4   8.8                                  Room Temp. (mm)                                                               Storage Stability @                                                                        OK/37   OK/37   OK/42 OK/33 OK/33                                Room Temp.                                                                    (Appearance/Days)                                                             Storage Stability @                                                                        OK/37   OK/37   OK/42 OK/33 OK/33                                120° F.                                                                (Appearance/Days)                                                             Storage Stability @                                                                        OK/37   OK/37   OK/42 OK/33 OK/33                                158° F.                                                                (Appearance/Days)                                                             ______________________________________                                    

Each of the emulsions identified in Table I are dry to the touch andcuttable.

Examples F and G which are identified in Table II below are prepared asfollows. The oxidizer phase contains 78.5% NH₄ NO₃, 10.7% NaNO₃, and10.8% H₂ O. The organic phase is prepared using the wax and oilindicated in Table II and the product of Example 1. The organic phase ismelted at 90° C. The oxidizer is heated to 104° C. The oxidizer is addedto the organic phase with stirring using a Sunbeam Mixmaster mixer at50-100% on the variac for one minute. The ratio of oxidizer to organicphase, viscosity, and the amount of additional mixing or working in theSunbeam Mixmaster mixer at 100% on the variac are indicated in Table II.Glass microbubbles (68-82 microns) are added to the hot emulsion at alevel of 42.5 grams of beads per 100 grams of emulsion.

                  TABLE II                                                        ______________________________________                                                         F        G                                                   ______________________________________                                        Product of Ex. 1,  20.4       20.0                                            (% of organic phase)                                                          Mineral oil,       20.4       20.0                                            (% of organic phase)                                                          50:50 blend of micro-                                                                            59.2       60.0                                            crystalline wax and                                                           paraffin wax,                                                                 (% of organic phase)                                                          Oxidizer/Organic phase ratio                                                                     95.2/4.9   95.0/5.0                                        Work, (min.)       6.0        1.5                                             Initial Viscosity, 142,000/   77,000/                                         (cPs/°F.)   166        180                                             ______________________________________                                    

Examples F and G are dry to the touch, cuttable, and stable at roomtemperature and after one hour at 90° C.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

I claim:
 1. An explosive composition comprising a discontinous oxidizerphase comprising at least one oxygen-supplying component, a continousorganic phase comprising at least one carbonaceous fuel, an anemulsifying amount of a composition comprising:(A) at least one saltmoiety derived from (A)(I) at least one high-molecular weightpolycarboxylic acylating agent, said acylating agent (A)(I) having atleast one hydrocarbyl substituent having an average of from about 20 toabout 500 carbon atoms, and (A)(II) ammmonia, at least one amine, atleast one alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound; (B) at least one salt moiety derived from(B)(I) at least one low-molecular weight polycarboxylic acylating agent,said acylating agent (B)(I) optionally having at least one hydrocarbylsubstituent having an average of up to about 18 carbon atoms, and(B)(II) ammonia, at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound;said components (A) and (B) being coupled together by (C) atleast one compound having (i) two or more primary amino groups, (ii) twoor more secondary amino groups, (iii) at least one primary amino groupand at least one secondary amino group, (iv) at least two hydroxylgroups or (v) at least one primary or secondary amino group and at leastone hydroxyl group.
 2. The composition of claim 1 wherein (A) (I) isderived from at least one alpha-beta olefinically unsaturated carboxlyicacid or acid-producing compound, said acid or acid-producing compoundcontaining up to about 20 carbon atoms exclusive of the carboxyl-basedgroups.
 3. The composition of claim 1 wherein (A) (I) is represented bythe formulae ##STR17## wherein R is said hydrocarbyl substituent of(A)(I).
 4. The composition of claim 1 wherein said hydrocarbylsubstituent of (A)(I) has an average of from about 30 to about 500carbon atoms.
 5. The composition of claim 1 wherein said hydrocarbylsubstituent of (A)(I) has an average of from about 40 to about 500carbon atoms.
 6. The composition of claim 1 wherein said hydrocarbylsubstituent of (A)(I) has an average of from about 50 to about 500carbon atoms.
 7. The composition of claim 1 wherein said hydrocarbylsubstituent of (A)(I) is an alkyl or an alkenyl group.
 8. Thecomposition of claim 1 wherein said hydrocarbyl substituent of (A)(I) isa poly(isobutylene) group.
 9. The composition of claim 1 whereincomponent (A)(II) comprises at least one monoamine.
 10. The compositionof claim 1 wherein component (A)(II) comprises at least one polyamine.11. The composition of claim 1 wherein component (A)(II) comprises atleast one primary, secondary and/or tertiary amine.
 12. The compositionof claim 1 wherein component (A)(II) comprises at least one aliphatic,cycloaliphatic and/or aromatic amine.
 13. The composition of claim 1wherein component (A)(II) comprises at least one alkylene polyamine ofthe formula ##STR18## wherein n is a number of from 1 to about 10, eachR is independently a hydrogen atom or a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, and the Alkylene group has from 1 to about 10 carbon atoms. 14.The composition of claim 1 wherein component (A)(II) comprises (a) atleast one N-(hydroxyl-substituted hydrocarbyl) amine, (b) at least onehydroxyl-substituted poly(hydrocarbyloxy) analog of (a), or (c) amixture of (a) and (b).
 15. The composition of claim 1 wherein component(A)(II) comprises at least one alkanol amine containing up to about 40carbon atoms.
 16. The composition of claim 1 wherein component (A)(II)is selected from the group consisting of (a) primary, secondary andtertiary alkanol amines which can be represented correspondingly by theformulae ##STR19## (b) hydroxyl-substituted oxyalkylene analogs of saidalkanol amines represented by the formulae ##STR20## wherein each R isindependently a hydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more of any of the above.
 17. The composition ofclaim 1 wherein component (A)(II) comprises dimethylethanolamine. 18.The composition of claim 1 wherein component (A)(II) comprises ammonia.19. The composition of claim 1 wherein component (A)(II) comprises atleast one alkali metal.
 20. The composition of claim 1 wherein component(A)(II) comprises sodium or potassium.
 21. The composition of claim 1wherein component (A)(II) comprises at least one alkaline earth metal.22. The composition of claim 1 wherein component (A)(II) comprises atleast one alkali metal oxide, hydroxide or carbonate.
 23. Thecomposition of claim 1 wherein component (A)(II) comprises at least onealkaline earth metal oxide, hydroxide or carbonate.
 24. The compositionof claim 1 wherein component (B)(I) is at least one compound selectedfrom the group consisting of maleic acid, maleic anhydride, chloromaleicanhydride, malonic acid, succinic acid, succinic anhydride, glutaricacid, glutaric anhydride, adipic acid, pimelic acid, azelaic acid,sebacic acid, glutaconic acid, citraconic acid, itaconic acid, allylsuccinic acid, cetyl malonic acid and tetrapropylene-substitutedsuccinic anhydride.
 25. The composition of claim 1 wherein (B)(I) isrepresented by the formulae ##STR21## wherein R is said hydrocarbylsubstituent of (B)(I).
 26. The composition of claim 1 wherein saidhydrocarbyl substituent of (B)(I) is derived from at least one compoundselected from the group consisting of ethylene, propylene, 1-butene,isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene,1-heptene, 1-octene, styrene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene and 1-octadecene.
 27. The composition of claim 1 whereinsaid hydrocarbyl substituent of (B)(I) is derived from at least onemember within alpha-olefin fraction selected from the group consistingof C₁₅₋₁₈ alpha-olefins, C₁₂₋₁₆ alpha-olefins, C₁₄₋₁₆ alpha-olefins,C₁₄₋₁₈ alpha-olefins and C₁₆₋₁₈ alpha-olefins.
 28. The composition ofclaim 1 wherein said hydrocarbyl substituent of (B)(I) has an average offrom about 8 to about 18 carbon atoms.
 29. The composition of claim 1wherein said hydrocarbyl substituent of (B)(I) has an average of fromabout 12 to about 18 carbon atoms.
 30. The composition of claim 1wherein said hydrocarbyl substituent of (B)(I) is an alkyl or an alkenylgroup.
 31. The composition of claim 1 wherein component (B)(II)comprises at least one monoamine.
 32. The composition of claim 1 whereincomponent (B)(II) comprises at least one polyamine.
 33. The compositionof claim 1 wherein component (B)(II) comprises at least one primary,secondary and/or tertiary amine.
 34. The composition of claim 1 whereincomponent (B)(II) comprises at least one aliphatic, cycloaliphaticand/or aromatic amine.
 35. The composition of claim 1 wherein component(B)(II) comprises at least one alkylene polyamine of the formula##STR22## wherein n is a number of from 1 to about 10, each R isindependently a hydrogen atom or a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, and the Alkylene group has from 1 to about 10 carbon atoms. 36.The composition of claim 1 wherein component (B)(II) comprises (a) atleast one N-(hydroxyl-substituted hydrocarbyl) amine, (b) at least onehydroxyl-substituted poly(hydrocarbyloxy) analog of (a), or (c) amixture of (a) and (b).
 37. The composition of claim 1 wherein component(B)(II) comprises at least one alkanol amine containing up to about 40carbon atoms.
 38. The composition of claim 1 wherein component (B)(II)is selected from the group consisting of (a) primary, secondary andtertiary alkanol amines which can be represented correspondingly by theformulae ##STR23## (b) hydroxyl-substituted oxyalkylene analogs of saidalkanol amines represented by the formulae ##STR24## wherein each R isindependently a hydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more thereof.
 39. The composition of claim 1wherein component (B)(II) comprises dimethylethanolamine.
 40. Thecomposition of claim 1 wherein component (B)(II) comprises ammonia. 41.The composition of claim 1 wherein component (B)(II) comprises at leastone alkali metal.
 42. The composition of claim 1 wherein component(B)(II) comprises sodium or potassium.
 43. The composition of claim 1wherein component (B)(II) comprises at least one alkaline earth metal.44. The composition of claim 1 wherein component (B)(II) comprises atleast one alkali metal oxide, hydroxide or carbonate.
 45. Thecomposition of claim 1 wherein component (B)(II) comprises at least onealkaline earth metal oxide, hydroxide or carbonate.
 46. The compositionof claim 1 wherein component (C) comprises at least one polyamine. 47.The composition of claim 1 wherein component (C) comprises at least onealiphatic, cycloaliphatic or aromatic polyamine.
 48. The composition ofclaim 1 wherein component (C) comprises at least one alkylene polyamineof the formula ##STR25## wherein n is a number in the range of from 1 toabout 10, each R and R' is independently hydrogen or a hydrocarbyl groupor a hydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, with the proviso that at least one of R and at least one of R'are hydrogen, and the Alkylene group has from 1 to about 10 carbonatoms.
 49. The composition of claim 1 wherein component (C) comprises atleast one polyol.
 50. The composition of claim 1 wherein component (C)comprises at least one compound represented by the formula

    R(OH).sub.m

wherein R is a monovalent or polyvalent organic group joined to the OHgroups through carbon-to-oxygen bonds and m is an integer of from 2 toabout
 10. 51. The composition of claim 1 wherein component (C) comprisesat least one polyhydroxy aromatic compound.
 52. The composition of claim1 wherein component (C) comprises ethylene glycol.
 53. The compositionof claim 1 wherein component (C) comprises at least one primary orsecondary hydroxyamine.
 54. The composition of claim 1 wherein component(C) comprises (a) at least one N-(hydroxyl-substituted hydrocarbyl)primary or secondary amine, (b) at least one hydroxyl-substitutedpoly(hydrocarbyloxy) analog of (a), or (c) a mixture of (a) and (b). 55.The composition of claim 1 wherein component (C) comprises at least oneprimary or secondary alkanol amine containing up to about 40 carbonatoms.
 56. The composition of claim 1 wherein component (C) is selectedfrom the group consisting of (a) primary and secondary alkanol amineswhich can be represented correspondingly by the formulae ##STR26## (b)hydroxyl-substituted oxyalkylene analogs of said alkanol aminesrepresented by the formulae ##STR27## wherein R is a hydrocarbyl groupof one to about 8 carbon atoms or a hydroxyl-substituted hydrocarbylgroup of 2 to about 8 carbon atoms and R' is a divalent hydrocarbylgroup of 2 to about 18 carbon atoms, and mixtures of two of morethereof.
 57. An explosive composition made by combining an oxidizerphase comprising at least one oxygen-supplying component with an organicphase comprising at least one carbonaceous fuel and a compositioncomprising:(A) at least one salat moiety derived from (A)(I) at leastone high-molecular weight polycarboxylic acylating agent, said acylatingagent (A)(I) having at least one hydrocarbyl substituent having anaverage of from about 20 to about 500 carbon atoms, and (A)(II) ammonia,at least one amine, at least one alkali or alkaline earth metal, and/orat least one alkali or alkaline earth metal compound; (B) at least onesalt moiety drived from (B)(I) at least one low-molecular weightpolycarboxylic acylating agent said acylating agent (B)(I) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms, and (B)(II) ammonia, at least one amine, at leastone alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound;said components (A) and (B) being coupledtogether by (C) at least one compound having (i) two or more primaryamino groups, (ii) two or more secondary amino groups, (iii) at leastone primary amino group and at least one secondary amino group, (iv) atleast two hydroxyl groups or (v) at least one primary or secondary aminogroup and at least one hydroxyl group.
 58. A cap-sensitive explosiveemulsion comprising a discontinous oxidizer phase comprising at leastone oxygen-supplying component, a continuous organic phase comprising atleast one carbonaceous fuel, said carbonaceous fuel comprising at leastone wax, and an emulsifying amount of a composition comprising:(A) atleast one salt moiety derived from (A)(I) at least one high-molecularweight polycarboxylic acylating agent, said acylating agent (A)(I)having at least one hydrocarbyl substituent having an average of fromabout 20 to about 500 carbon atoms, and (A)(II) ammonia, at least oneamine, at least one alkali or alkaline earth metal, and/or at least onealkali or alkaline earth metal compound; (B) at least one salt moietyderived from (B)(I) at least one low-molecular weight polycarboxylicacylating agent, said acylating agent (B)(I) optionally having at leastone hydrocarbyl substituent having an average of up to about 18 carbonatoms, and (B)(II) ammonia, at least one amine, at least one alkali oralkaline earth metal, and/or at least one alkali or alkaline earth metalcompound; said components (A) and (B) being voupled together by (C) atleast one compound having (i) two to more primary amino groups, (ii) twoor more secondary amino groups, (iii) at least one primary amino groupand at least one secondary amino group, (iv) at least two hydroxylgroups or (v) at least one primary or secondary amino group and at leastone hydroxyl group.
 59. A cartridge comprising a cartridge casingcontaining at least one cap-sensitive explosive emulsion, said emulsioncomprising a discontinous oxidizer phase comprising at least oneoxygen-supplying component, a continuous organic phase comprising atleast one carbonaceous fuel, and an emulsifying amount of a compositoncomprising:(A) at least one salt moiety drived from (A)(I) at least onehigh-molecular weight polycarboxylic acylating agent, said acylatingagent (A)(I) having at least one hydrocarbyl substituent having anaverage of from about 20 to about 500 carbon atoms, and (A)(II) ammonia,at least one amine, at least one alkali or alkaline earth metal, and/orat least one alkali or alkaline earth metal compound; (B) at least onesalt moiety derived from (B)(I) at least one low-molecular weightpolycarboxylic acylating agent, said acylating agent (B)(I) optionallyhaving at least one hydrocarbyl substituent having an average of up toabout 18 carbon atoms, and (B)(II) ammonia, at least one amine, at leastone alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound; said components (A) and(B) being coupledtogether by (C) at least one compound having (i) two or more primaryamino groups, (ii) two or more secondary amino groups, (iii) at leastone primary amino group and at least one secondary amino group, (iv) atleast two hydroxyl groups or (v) at least one primary or secondary aminogroup and at least one hydroxyl group.
 60. A cartridge having a diameterof about 1.25 inches or less comprising at least one cap-sensitiveexplosive emulsion, said emulsion comprising a discontinuous oxidizerphase comprising at least one oxygen-supplying component, a continuousorganic phase comprising at least one carbonaceous fuel, and anemulsifying amount of a composition comprising:(A) at least one saltmoiety derived from (A)(I) at least one high-molecular weightpolycarboxylic acylating agent, said acylating agent (A)(I) having atleast one hydrocarbyl substituent having an average of from about 20 toabout 500 carbon atoms, and (A)(II) ammonia, at least one amine, atleast one alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound; (B) at least one salt moiety derived from(B)(I) at least one low-molecular weight polycarboxylic acylating agent,said acylating agent (B)(I) optionally having at least one hydrocarbylsubstituent having an average of up to about 18 carbon atoms, and(B)(II) ammonia, at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound; said components (A) and (B) being coupled together by (C) atleast one compound having (i) two or more primary amino groups, (ii) twoor more secondary amino groups, (iii) at least one primary amino groupand at least one secondary amino group, (iv) at least two hydroxylgroups or (v) at least one primary or secondary amino group and at leastone hydroxyl group.